EP2157202B1 - Hitzebeständiger ferritstahl - Google Patents

Hitzebeständiger ferritstahl Download PDF

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EP2157202B1
EP2157202B1 EP08764663.4A EP08764663A EP2157202B1 EP 2157202 B1 EP2157202 B1 EP 2157202B1 EP 08764663 A EP08764663 A EP 08764663A EP 2157202 B1 EP2157202 B1 EP 2157202B1
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haz
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steel
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EP2157202A1 (de
EP2157202A4 (de
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Hiroyuki Hirata
Mitsuru Yoshizawa
Kazuhiro Ogawa
Masaaki Igarashi
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Nippon Steel Corp
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Nippon Steel and Sumitomo Metal Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/30—Ferrous alloys, e.g. steel alloys containing chromium with cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese

Definitions

  • the present invention relates to a heat resistant ferritic steel excellent in the high-temperature strength and weld crack resistance in a weld heat-affected zone, which is used as members for high temperature services, such as thermal power generation boilers.
  • Patent Document 1 and Patent Document 2 For heat resistant ferritic steels, efforts have been made to increase strength in order to cope with severer steam conditions in the future.
  • Patent Document 3 proposes a steel strengthened by a fine intermetallic compound phase with the addition of W and Mo.
  • Patent Document 4 proposes a steel having improved strength by using the phase of M 23 C 6 -based carbides and intermetallic compounds which precipitate at the martensite lath interface.
  • Patent Document 5 discloses a steel whose long-time creep strength of joints is improved by producing Ti-, Zr- and Hf-based nitrides which are stable in spite of weld heat input;
  • Patent Document 6 discloses a steel similarly improved by adding W and causing (Nb, Ta) carbo-nitrides to finely precipitate.
  • Patent Document 7 and Patent Document 8 disclose steels similarly improved by suppressing the formation of Cr carbides and increasing the long-time stability of fine carbo-nitrides, such as V and Nb.
  • Patent Document 9 proposes a method that involves suppressing the grain refinement in the HAZ by adding 0.003 to 0.03% of B, thereby improving the creep strength in the HAZ.
  • B is known well as an element having such an effect
  • B is also known well as an element that increases the susceptibilities of the solidification cracking in a weld metal and also of the liquation cracking in its HAZ.
  • the problem is that when the steel is used as thick wall members in main steam pipes for boilers, pressure vessels and the like, this steel does not have sufficient weldability (weld crack resistance).
  • EP1304394 (A1 ) discloses a ferritic heat-resisting steel that shows a slight decrease in creep strength at the heat affected zone of the welded joint.
  • the steel is characterized by consisting of, by mass %, C: less than 0.05%, Si: not more than 1.0%, Mn: not more than 2.0%, P: not more than 0.030%, S: not more than 0.015%, Cr: 7 - 14 %, V: 0.05 - 0.40 %, Nb: 0.01 - 0.10 %, N: not less than 0.001% but less than 0.050%, sol.
  • Al not more than 0.010%
  • O (oxygen) not more than 0.010%
  • the balance being Fe and impurities, and further characterized in that the density of carbide and carbonitride precipitates contained with a grain diameter of not less than 0.3 ⁇ m is not more than 1 x 10 6 /mm 2 .
  • heat resistant ferritic steels have the advantage of small coefficients in thermal expansion in addition to inexpensiveness as described above, it is expected that these steels are used in welded structures in thermal power generation boilers and the like for which efforts are being made toward higher temperature and higher pressure steam conditions.
  • the present invention has been made in view of such a situation, and its objective is to provide a heat resistant ferritic steel which is excellent in the weld crack resistance of the HAZ and is also superior in creep strength.
  • the heat resistant ferritic steel in accordance with the present invention. sets a target value of rupture time for the creep strength in the HAZ of not less than three times, and preferably not less than five times that of conventional steels.
  • B is an element which is apt to segregate at the grain boundaries and also lowers melting points significantly.
  • S and P are elements that are apt to undergo grain-boundary segregation and also lower melting points significantly.
  • the liquation cracking in the HAZ is related to the composition of the steel used, and this constitutes a significant restriction in actual use.
  • the inventors earnestly examined the requirements in order to be able to prevent the liquation cracking of the HAZ and also to increase the strength of the HAZ.
  • C acts as a melting point lowering element and increases the liquation cracking susceptibility in the HAZ by adding to the above-described melting point lowering action of B. For this reason, the inventors considered that it becomes possible to reduce the lowering of a melting point by lowering the C content according to the B content.
  • C has an effect on the free energy in the formation of sulfides and phosphides through its interaction with them. That is, at high temperatures, the solubility of sulfides or phosphides of Cr, Nd and the like decreases with increasing C content, and when the C content further increases, the solubility of these sulfides or phosphides has a tendency to increase again. When the solubility of sulfides and phosphides increases, the amounts of S and P increase, which segregate at the grain boundaries due to the thermal effect of welding and the like, and the liquation cracking susceptibility increases.
  • the inventors obtained the new knowledge that adding B and lowering content of C results in preventing liquation cracking, and also results in improving more the creep strength in the HAZ, when compared to the case of adding B but not lowered content of C.
  • the lowering content of C to a prescribed range decreases the amount of carbides present at the grain boundaries.
  • the pinning effect is small even when heating is performed to a temperature between the Ac 1 transformation point and the Ac 3 transformation point, and the austenitic phase forms nuclei at the grain boundaries and, therefore, crystal grains are apt to coarsen readily.
  • the grain refinement suppressing effect in the HAZ increases due to the combined effect of the nucleation suppression by the addition of B.
  • the degree of strengthening of the creep strength may increase, when compared to the case of adding B but not lowered content of C.
  • the lower limit to the C content should be set at 0.005% or more in order to have the strength improving effect.
  • the B content be 0.005 to 0.025% and that the condition given by 0.005 ⁇ C ⁇ (-5/3) ⁇ [%B] + 0.085 be satisfied.
  • the heat resistant ferritic steel in accordance with the present invention is excellent in the weld crack resistance in the HAZ and has superior creep strength in the HAZ.
  • C (carbon) along with B is an important element in the present invention.
  • C is an essential element because C forms carbides and contributes to ensuring high-temperature strength, and because C is an element effective in obtaining a martensitic microstructure.
  • C segregates at the grain boundaries, C promotes to lower the melting point at the grain boundaries along with the effect of B, S and P and is indirectly responsible for the formation of sulfides and phosphides in the coarse-grained HAZ. Thereby it has an exerting effect on the liquation cracking susceptibility.
  • C content is lowered, in the fine-grained HAZ, C has an improved creep strength due to the effects of the promotion of crystal grain coarsening during transformation and the suppression of the growth of fine carbides.
  • the lowering of the melting point at the grain boundaries is caused by the C itself, and it is suppressed.
  • Stable sulfides and phosphides are formed in the coarse-grained HAZ, whereby liquation cracking is prevented by suppressing the lowering of the melting point which is caused by the grain-boundary segregation of S and P, and at the same time the creep strength of a fine-grained HAZ is improved.
  • the B content is defined in a specific range and it is necessary that the C content be in the range of 0.005% or more and ⁇ (-5/3) ⁇ [%B] + 0.085 ⁇ % or less.
  • a preferred lower limit of the C content is 0.010%.
  • Si more than 0.1% and not more than 1.0%
  • Si silicon is added in amounts exceeding 0.1% as a deoxidizer. However, if Si is added excessively, this causes the deterioration of creep ductility and toughness, so the upper limit is 1.0%, preferably 0.8%.
  • the Si content is more preferably in the range of more than 0.2% and not more than 0.7%.
  • Mn 2.0% or less and 0.01 % or more
  • Mn manganese
  • Mn content is 2.0% or less.
  • the Mn content is preferably 1.8% or less.
  • 0.01% or more of Mn is added.
  • Co is an austenite former and is an element necessary for the martensitizing of a matrix. To obtain this effect, it is necessary that 1% or more of Co be added. However, if Co is added in an amount exceeding 8%, this causes a remarkable decrease in creep ductility.
  • the Co content is preferably in the range of over 2% and 7% or less.
  • Cr chromium
  • Cr is an element essential for ensuring oxidation resistance and high-temperature corrosion resistance in heat resistant steels and for obtaining a martensitic microstructure of a matrix in a stable manner. To obtain this effect, it is necessary that 7% or more of Cr be added. However, if Cr is added excessively, this lowers the stability of carbides caused by the formation of a large amount of Cr carbides, which results in decreases in creep strength and toughness. For this reason, it is necessary that the Cr content be 13% or less.
  • the Cr content is preferably in the range of 8 to 12%, more preferably in the range of 8 to 10%.
  • V 0.05 to 0.4%
  • V vanadium
  • Nb vanadium
  • V vanadium
  • the V content is preferably in the range of 0.10 to 0.35%.
  • Nb niobium
  • V niobium
  • Nb is an element which, along with V, forms stable fine carbo-nitrides at temperatures up to high levels in the grains and contributes significantly to the improvement of creep strength.
  • Nb is added excessively, this results in an increase in the growth rate of carbo-nitrides, which causes an early loss of the dispersion strengthening effect, and also this results in a decrease in toughness. Therefore, it is necessary that the Nb content be 0.09% or less.
  • Mo (molybdenum) and W (tungsten) are elements which perform the solid-solution strengthening of a matrix and contribute to the improvement of creep strength. To obtain this effect, it is necessary that either one or both of Mo and W be added in amounts of 0.5% or more as a total. However, if these elements are added excessively in amounts exceeding 4%, this forms coarse intermetallic compounds and results in an extreme decrease in toughness. Also, when W is singly added, it is preferred that the lower limit of the W content be 1%.
  • B (boron) along with C is an important element in the present invention.
  • B segregates at the grain boundaries in the HAZ and lowers the grain-boundary energy, thereby delaying the nucleation of the austenitic phase and suppressing grain refinement. To obtain this effect sufficiently, it is necessary that at least 0.005% or more of B be added.
  • B that segregates at the grain boundaries promotes lowering the melting point of the grain boundaries and causes liquation cracking to occur by adding to the effect of the segregation of S and P. To prevent this, it is necessary that the C content be defined in the above-described range.
  • the B content exceeds 0.025%, the HAZ creep strength improving effect becomes saturated and it is impossible to prevent liquation cracking even when the C content is defined in the above-described range. It is preferred that the lower limit of the B content be 0.007% or more. A more preferred range of the B content is from over 0.01% to 0.02% or less.
  • N nitrogen
  • V and Nb are elements which forms fine carbo-nitrides including V and Nb and is effective in ensuring creep strength. To obtain this effect, it is necessary that 0.003% or more of N be added. However, if N is added excessively, this results in an increase in the precipitation amount of carbo-nitrides and causes embrittlement. For this reason, the upper limit of the N content is 0.06%.
  • Al aluminum
  • the upper limit of the Al content is 0.03%.
  • the upper limit of the Al content is preferably 0.02% or less.
  • 0.001% or more of Al be added, although no lower limit is set.
  • O oxygen
  • Oxgen exists as an impurity. However, if a large amount of O is contained, this forms a large amount of oxides, deteriorating workability and ductility. For this reason, it is necessary that the O content be 0.02% or less.
  • P phosphorus
  • S and B segregates at the grain boundaries in a coarse-grained HAZ, and this results in liquation cracking by lowering the melting point.
  • C, Nb, S and B be defined in prescribed ranges and that the P content be 0.03% or less.
  • S sulfur
  • C, Nb, S and P be defined in prescribed ranges and that the S content be 0.02% or less.
  • Nd (neodymium) has a strong affinity for P and S. Nd forms compounds with S and P at the grain boundaries of a coarse-grained HAZ, thereby suppressing lowering of the melting point by S and P and preventing the liquation cracking of the HAZ. At the same time, Nd is effective in improving the HAZ creep ductility by reducing the grain-boundary embrittlement by S and P during use at high temperatures. Therefore, Nd may be added as required. However, because of a strong affinity for oxygen, if Nd is added excessively, this forms extra oxides and results in a decrease in the toughness of the HAZ. For this reason, the upper limit of the Nd content is 0.08%. A desirable upper limit is 0.06%. Incidentally, to positively obtain the above-described effect of the addition of Nd, it is preferred that 0.005% or more of Nd be added. It is more preferred that 0.015% or more of Nd be added.
  • Ta Like V and Nb, Ta (tantalum) forms stable fine carbides at temperatures up to high levels and contributes significantly to the improvement of creep strength. Therefore, Ta may be added as required. However, if Ta is added excessively, this results in an increase in the growth rate of carbides, bringing about early loosing of the dispersion strengthening effect, and also this results in a decrease in toughness. Therefore, the upper limit of the Ta content is 0.08% or less. Incidentally, to obtain the above-described effect of the addition of Ta, it is preferred that 0.005% or more of Ta be added.
  • Ca (calcium) is an element which improves the hot workability of steel, and when it is necessary to improve hot workability, Ca can be added. However, if the Ca content exceeds 0.02%, this results in the coarsening of inclusions, thereby contrastively impairing workability and toughness. Therefore, the upper limit of the Ca content is 0.02%. In order to obtain the above-described effect of the addition of Ca, it is preferred that 0.0003% or more of Ca be added. A more preferred range of the Ca content is from 0.001 % to 0.01 %.
  • Mg manganese
  • Ca manganese
  • Mg manganese
  • the upper limit of the Mg content is 0.02%.
  • a more preferred range of the Ca content is from 0.001% to 0.01 %.
  • the sixteen kinds of steels having the chemical compositions shown in Table 1 were melted in a vacuum furnace, and were then cast and rolled. Thereafter, the steels were normalized by air cooling after being held for 1 hour at 1150°C and were tempered by air cooling after being held for 1.5 hours at 770°C, whereby the steels were heat treated.
  • No. 13 denotes a steel corresponding to SUS410J3TB, which is a conventional steel. This steel was used as a comparative steel related to creep strength.
  • Steel plates 12 mm in thickness, 50 mm in width and 300 mm in length and steel plates 10 mm in thickness, 100 to 120 mm in width and 300 to 500 mm in length were fabricated by machining.
  • the longitudinal Varestraint test is a method of evaluating the liquation cracking susceptibility of the HAZ which involves, as schematically shown in Figure 1 , performing bead-on-plate welding in the longitudinal direction of a steel plate by using GTA welding, adding a strain due to bending by loading a force F at an end of the steel plate during the welding, thereby forcedly generating cracks in the HAZ, and measuring the total length of the cracks.
  • the welding conditions were 200 A ⁇ 15 V ⁇ 10 cm/min.
  • the amount of added strain was 4%. Steel plates in which liquation cracking did not occur in the HAZ were accepted.
  • test material 10 mm in thickness, 10 mm in width and 100 mm in length was sampled from a 10 mm thick steel plate.
  • a HAZ-simulated thermal cycle was given to the test material and the test material was heated to 1000°C, at which a strength decrease in the HAZ is especially remarkable, for 5 seconds.
  • the test material was subjected to post-weld heat treatment by air cooling at 740°C for 30 minutes, and creep test specimens were taken. The creep test was performed at a temperature of 650°C and stress of 117.7 MPa.
  • Table 2 shows the weld crack length (mm) in the longitudinal Varestraint test and the rupture time (hr) in the creep test.
  • Table 2 No. Cracking length in Varestraint test (mm) HAZ-sumulated thermal cycle material Creep rupture time (hr) 1 0.4* - 2 0.7* - 3 0 7327 4 0 6074 5 0 5862 6 0 3822 7 0 1584* 8 0 2211* 9 0 7207 10 0 2536 11 0 6980 12 0 2306* 13 - 829 14 0 4463 (not ruptured) 15 0 4463 (not ruptured) 16 0.6* - * out of scope of the invention
  • the creep rupture time of the HAZ did not satisfy the target value.
  • the creep rupture time of the HAZ did not satisfy the target value although the C content satisfies Expression (1).
  • the creep rupture time of the HAZ was still lower than that of the material of No. 8.
  • the heat resistant ferritic steel in accordance with the present invention, provides heat resistant ferritic steels, excellent in the weld crack resistance and creep strength of the HAZ, the heat resistant ferritic steel can be used in welded structures in thermal power generation boilers in which efforts are being made toward higher temperature and higher pressure steam conditions.
  • Figure 1 shows a longitudinal Varestraint test method.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)

Claims (1)

  1. Hoch-Cr hitzebeständiger Ferritstahl, dadurch gekennzeichnet, dass er, in Masse-%, aus Si: mehr als 0,1% und nicht mehr als 1,0%, Mn: 0,01 bis 2,0%, Co: 1 bis 8%, Cr: 7 bis 13%, V: 0,05 bis 0,4%, Nb: 0,01 bis 0,09%, entweder einem oder beiden von Mo und W: 0,5 bis 4% als eine Gesamtmasse, B: 0,005 bis 0,025%, Al: 0,03% oder weniger, und N: 0,003 bis 0,06%, Nd: 0,005 bis 0,08% besteht und C in einer Ausdruck (1) erfüllenden Menge enthält, optional ein oder mehr von Ta: 0,08% oder weniger, Ca: 0,02% oder weniger und Mg: 0,02% oder weniger enthält, und der Rest Eisen und Verunreinigungen ist, und O, P und S als Verunreinigungen jeweils derart sind, dass O: 0,02% oder weniger, P: 0,03% oder weniger und S: 0,02% oder weniger sind, 0 , 005 ≤ C ≤ − 5 / 3 × B + 0 , 085
    Figure imgb0003
     in welcher C und B den Gehalt von jedem Element (Masse-%) darstellen.
EP08764663.4A 2007-06-04 2008-05-26 Hitzebeständiger ferritstahl Active EP2157202B1 (de)

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PCT/JP2008/059630 WO2008149703A1 (ja) 2007-06-04 2008-05-26 フェライト系耐熱鋼

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CN103525984A (zh) * 2013-09-26 2014-01-22 无锡阳工机械制造有限公司 一种耐热钢的热处理方法
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KR102058602B1 (ko) 2015-12-18 2019-12-23 닛폰세이테츠 가부시키가이샤 페라이트계 내열강용 용접 재료, 페라이트계 내열강용 용접 조인트 및 페라이트계 내열강용 용접 조인트의 제조 방법
EP3480331A4 (de) * 2016-06-29 2020-01-01 Nippon Steel Corporation Ferritischer hitzefester stahl und ferritische wärmeübertragungsteil
CN108950148B (zh) * 2018-07-30 2020-07-21 钢铁研究总院 提高g115钢大口径厚壁管径向组织和性能均匀性方法
EP3892410A4 (de) 2018-12-05 2022-05-11 Nippon Steel Corporation Verfahren zur herstellung einer ferritischen hitzebeständigen stahlschweissverbindung
US20220235445A1 (en) * 2019-03-19 2022-07-28 Nippon Steel Corporation Ferritic heat-resistant steel

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EP2157202A1 (de) 2010-02-24
WO2008149703A1 (ja) 2008-12-11
EP2157202A4 (de) 2011-09-14
US20100086430A1 (en) 2010-04-08
KR20090130334A (ko) 2009-12-22
JPWO2008149703A1 (ja) 2010-08-26
JP5206676B2 (ja) 2013-06-12
CN101680065A (zh) 2010-03-24
CN101680065B (zh) 2011-11-16

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